Method of preparing a molecular sieve composition

ABSTRACT

This disclosure provides a method of preparing a crystalline molecular sieve comprising: (a) providing a reaction mixture comprising at least one source of ions of tetravalent element Y, at least one source of alkali metal hydroxide, water, optionally at least one seed crystal, and optionally at least one source of ions of trivalent element X, the reaction mixture having the following molar composition:
         Y:X 2 =2 to infinity, preferably from about 2 to about 1000,   OH − :Y=0.001 to 2, preferably from 0.1 to 1,   M + :Y=0.001 to 2, preferably from 0.01 to 2
 
wherein M is an alkali metal and the amount of water is at least sufficient to permit extrusion of the reaction mixture, wherein the reaction mixture is substantially free of crystalline molecular sieve; (b) extruding the reaction mixture to form a pre-formed extrudate; and (c) crystallizing the pre-formed extrudate in a liquid medium comprising water under liquid phase crystallization conditions to form a crystallized extrudate having the crystalline molecular sieve.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage filing of International PatentCooperation Treaty Application No. PCT/US2008/78315 filed Sep. 30, 2008,which claims the benefit of and priority to U.S. Provisional patentapplication Ser. Nos. 60/982,982, filed Oct. 26, 2007, and 60/982,945,filed Oct. 26, 2007.

FIELD OF THE INVENTION

The present disclosure relates to methods of preparing molecular sievecompositions, particularly but not exclusively, to method forcrystallizing pre-formed extrudates in a liquid medium comprising waterunder liquid phase crystallization conditions.

BACKGROUND OF THE INVENTION

Molecular sieve materials, both natural and synthetic, have catalyticproperties for various types of hydrocarbon conversion. Certainmolecular sieves (e.g., zeolites, AlPOs, and/or mesoporous materials)are ordered, porous crystalline materials having a definite crystallinestructure. Within the crystalline molecular sieve material there are alarge number of cavities which may be interconnected by a number ofchannels or pores. These cavities and pores are uniform in size within aspecific molecular sieve material. Since the dimensions of these poresare such as to accept for adsorption molecules of certain dimensionswhile rejecting those of larger dimensions, these materials have come tobe known as “molecular sieves” and are utilized in a variety ofindustrial processes.

Such molecular sieves, both natural and synthetic, include a widevariety of positive ion-containing crystalline oxides of tetravalentelement. These oxides of tetravalent element can be described as a rigidthree-dimensional framework of YO₄ and a trivalent element oxide, suchas a Group 13 element oxide (e.g., AlO₄) (as defined in the PeriodicTable, Chemical and Engineering News, 63(5), 27 (1985)). The tetrahedraare cross-linked by the sharing of oxygen atoms whereby the ratio of thetotal trivalent element (e.g., aluminum) and tetravalent atoms to oxygenatoms is 1:2. The electrovalence of the tetrahedra containing thetrivalent element (e.g., aluminum) is balanced by the inclusion in thecrystal of a cation, for example a proton, an alkali metal or analkaline earth metal cation. This can be expressed as the ratio of thetrivalent element (e.g., aluminum) to the number of various cations,such as H⁺, Ca²⁺/2, Sr²⁺/2, Na⁺, K⁺, or Li⁺, being equal to unity.

Molecular sieves that find application in catalysis include any of thenaturally occurring or synthetic crystalline molecular sieves. Examplesof these sieves include large pore zeolites, intermediate pore sizezeolites, and small pore zeolites. These zeolites and their isotypes aredescribed in “Atlas of Zeolite Framework Types”, eds. W. H. Meier, D. H.Olson and Ch. Baerlocher, Elsevier, Fifth Edition, 2001, which is hereinincorporated by reference. A large pore zeolite generally has a poresize of at least about 7 Å and includes LTL, VFI, MAZ, FAU, OFF, *BEA,and MOR framework type zeolites (IUPAC Commission of ZeoliteNomenclature). Examples of large pore zeolites include mazzite,offretite, zeolite L, VPI-5, zeolite Y, zeolite X, omega, and zeolitebeta. An intermediate pore size zeolite generally has a pore size fromabout 5 Å to less than about 7 Å and includes, for example, MFI, MEL,EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON framework type zeolites(IUPAC Commission of Zeolite Nomenclature). Examples of intermediatepore size zeolites include ZSM-5, ZSM-11, ZSM-22, “MCM-22 familymaterial”, silicalite 1, and silicalite 2. A small pore size zeolite hasa pore size from about 3 Å to less than about 5.0 Å and includes, forexample, CHA, ERI, KFI, LEV, SOD, and LTA framework type zeolites (IUPACCommission of Zeolite Nomenclature). Examples of small pore zeolitesinclude ZK-4, ZSM-2, SAPO-34, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22,ZK-5, ZK-20, zeolite A, chabazite, zeolite T, gmelinite, ALPO-17, andclinoptilolite.

The term “MCM-22 family material” (or “material of the MCM-22 family” or“molecular sieve of the MCM-22 family”), as used herein, includes one ormore of:

-   (i) molecular sieves made from a common first degree crystalline    building block unit cell, which unit cell has the MWW framework    topology. (A unit cell is a spatial arrangement of atoms which if    tiled in three-dimensional space describes the crystal structure.    Such crystal structures are discussed in the “Atlas of Zeolite    Framework Types”, Fifth edition, 2001, the entire content of which    is incorporated as reference);-   (ii) molecular sieves made from a common second degree building    block, being a 2-dimensional tiling of such MWW framework topology    unit cells, forming a monolayer of one unit cell thickness,    preferably one c-unit cell thickness;-   (iii) molecular sieves made from common second degree building    blocks, being layers of one or more than one unit cell thickness,    wherein the layer of more than one unit cell thickness is made from    stacking, packing, or binding at least two monolayers of one unit    cell thickness. The stacking of such second degree building blocks    can be in a regular fashion, an irregular fashion, a random fashion,    or any combination thereof; and-   (iv) molecular sieves made by any regular or random 2-dimensional or    3-dimensional combination of unit cells having the MWW framework    topology.

The MCM-22family materials are characterized by having an X-raydiffraction pattern including d-spacing maxima at 12.4±0.25, 3.57±0.07and 3.42±0.07 Angstroms (either calcined or as-synthesized). The MCM-22family materials may also be characterized by having an X-raydiffraction pattern including d-spacing maxima at 12.4±0.25, 6.9±0.15,3.57±0.07 and 3.42±0.07 Angstroms (either calcined or as-synthesized).The X-ray diffraction data used to characterize the molecular sieve areobtained by standard techniques using the K-alpha doublet of copper asthe incident radiation and a diffractometer equipped with ascintillation counter and associated computer as the collection system.Materials belong to the MCM-22 family include MCM-22 (described in U.S.Pat. No. 4,954,325 and U.S. patent application Ser. No. 11/823,722 nowU.S. Pat. No. 7,883,686), PSH-3 (described in U.S. Pat. No. 4,439,409),SSZ-25 (described in U.S. Pat. No. 4,826,667), ERB-1 (described inEuropean Patent No. 0293032), ITQ-1 (described in U.S. Pat. No.6,077,498), ITQ-2 (described in International Patent Publication No.W097117290), ITQ-30 (described in International Patent Publication No.W02005118476), MCM-36 (described in U.S. Pat. No. 5,250,277), MCM-49(described in U.S. Pat. No. 5,236,575), UZM-8 described in U.S. Pat. No.6,756,030), MCM-56 (described in U.S. Pat. No. 5,362,697), EMM-10-P(described in U.S. patent application Ser. No. 11/823,129 now U.S. Pat.No. 7,959,899), and EMM-10 (described in U.S. patent application Ser.No. 11/824,742 now U.S. Pat. No. 8,110,176 and Ser. No. 11/827,953 nowU.S. Pat. No. 7,842,277). The entire contents of the patents areincorporated herein by reference.

It is to be appreciated the MCM-22 family molecular sieves describedabove are distinguished from conventional large pore zeolite alkylationcatalysts, such as mordenite, in that the MCM-22 materials have 12-ringsurface pockets which do not communicate with the 10-ring internal poresystem of the molecular sieve.

The zeolitic materials designated by the IZA-SC as being of the MWWtopology are multi-layered materials which have two pore systems arisingfrom the presence of both 10 and 12 membered rings. The Atlas of ZeoliteFramework Types classes five differently named materials as having thissame topology: MCM-22, ERB-1, ITQ-1, PSH-3, and SSZ-25.

The MCM-22 family molecular sieves have been found to be useful in avariety of hydrocarbon conversion processes. Examples of MCM-22 familymolecular sieve are MCM-22, MCM-49, MCM-56, ITQ-1, PSH-3, SSZ-25, andERB-1. Such molecular sieves are useful for alkylation of aromaticcompounds. For example, U.S. Pat. No. 6,936,744 discloses a process forproducing a monoalkylated aromatic compound, particularly cumene,comprising the step of contacting a polyalkylated aromatic compound withan alkylatable aromatic compound under at least partial liquid phaseconditions and in the presence of a transalkylation catalyst to producethe monoalkylated aromatic compound, wherein the transalkylationcatalyst comprises a mixture of at least two different crystallinemolecular sieves, wherein each of said molecular sieves is selected fromzeolite beta, zeolite Y, mordenite and a material having an X-raydiffraction pattern including d-spacing maxima at 12.4±0.25, 6.9±0.15,3.57±0.07 and 3.42±0.07 Angstrom (Å).

The MCM-22 family molecular sieves including MCM-22, MCM-49, and MCM-56have various applications in hydrocarbon conversion processes.Unfortunately, industrial applications of zeolite catalysts have beenhindered due to some major disadvantages associated with the currentsynthesis techniques that make large scale production of these catalystscomplicated and therefore expensive. At present, crystalline zeolitecatalysts are synthesized mainly by conventional liquid-phasehydrothermal treatment, including in-situ crystallization and seedingmethod, and the vapor phase transport method.

In the hydrothermal method, a reaction mixture of silica, alumina,caustic agent, an organic template or structure directing agent, andwater is heated at a high temperature in a liquid phase to producecrystalline zeolite crystals (e.g., described in U.S. Pat. No.5,871,650). The product is recovered by filtration and washing followedby calcination.

U.S. Pat. No. 5,558,851 discloses a method for preparing a crystallinealuminosilicate zeolite from a reaction mixture containing onlysufficient water so that the reaction mixture may be shaped if desired.In the method, the reaction mixture is heated at crystallizationconditions and in the absence of an external liquid phase, so thatexcess liquid need not be removed from the crystallized material priorto drying the crystals.

U.S. Pat. No. 6,099,820 discloses a method for preparing a crystallinezeolite having the X-ray diffraction lines of Table 1 of the U.S. Pat.No. 6,099,820. The method includes preparing a template-free reactionmixture including at least one active source of a first oxide selectedfrom the group consisting of an oxide of silicon, germanium or both,optionally at least one active source of a second oxide selected fromthe group consisting of an oxide of aluminum, boron, gallium, iron or amixture thereof; and heating the reaction mixture at crystallizationconditions for sufficient time to form a crystallized materialcontaining zeolite crystals having the X-ray diffraction lines of Table1 of the U.S. Pat. No. 6,099,820, where said zeolite crystals have afirst oxide/second oxide molar ratio greater than 12.

U.S. Pat. Nos. 5,665,325, 6,864,203, 6,039,864, 6,958.305, and 6,977,320disclose a binder-free zeolite (or zeolite-bound-zeolite) process forproducing substantially binder-free zeolites, and the use of thesezeolites in catalysis and in separation processes.

U.S. Pat. No. 5,871,650 discloses a new zeolite membrane which exhibitsa columnar cross-sectional morphology and preferred crystallographicorientation comprising a porous substrate having coated thereon amesoporous growth enhancing layer and a layer of columnar zeolitecrystals on said mesoporous growth enhancing layer, and wherein saidmesoporous growth enhancing layer comprises nanocrystalline or colloidalsized zeolites, nanocrystalline or colloidal zeolite and metal oxide, ornanocrystalline or colloidal zeolite and colloidal metal, ornanocrystalline or colloidal zeolite, colloidal metal and metal oxide,and wherein said mesoporous growth enhancing layer has interstices ofabout 20 to about 2000 Å, and wherein said columnar zeolite layer is apolycrystalline layer wherein 99.9% of said columnar zeolite crystalshave at least one point between adjacent crystals that is <20 Å. Thisdisclosure is further directed to a process of producing a zeolitemembrane exhibiting a columnar crystallographic orientation.

U.S. Pat. No. 5,895,769 discloses a new zeolite containing compositionand a process for preparing the same. The composition is unique in thatthe zeolite crystals making up one layer of the composition pack in amanner such that the composition is essentially continuous with no largescale voids even when the zeolite layer is <10 μm thick. This disclosureis directed toward a composition comprised of a porous substrate and alayer of zeolite crystals wherein said layer of zeolite crystals is apolycrystalline layer with at least 99% of said zeolite crystals havingat least one point between adjacent crystals that is ≦20 Å and whereinat least 90% of said crystals have widths of from about 0.2 to about 100microns (preferably about 2 to about 50 microns) and wherein at least75% of said crystals have a thickness of within 20% of the averagecrystal thickness. Preferably the composition has at most 1 volume %voids in the zeolite layer. Use of the composition is also described.

U.S. Pub. 2007-0191658 A1 discloses an improved vapor phasecrystallization process by:

-   (a) providing a reaction mixture comprising at least one source of    ions of tetravalent element Y, at least one source of alkali metal    hydroxide, water, optionally at least one seed crystal, and    optionally at least one source of ions of trivalent element X, said    reaction mixture having the following mole composition:    -   Y:X₂=10 to infinity    -   OH⁻:Y=0.001 to 2    -   M⁻:Y=0.001 to 2    -   wherein Y is a tetravalent element, X is a trivalent element, M        is an alkali metal and the amount of water is at least        sufficient to permit extrusion of said reaction mixture;-   (b) extruding said reaction mixture to form a pre-formed extrudate;    and-   (c) crystallizing said pre-formed extrudate under vapor phase    conditions in a reactor to form said crystalline molecular sieve    whereby excess alkali metal hydroxide is removed from the pre-formed    extrudate during crystallization.

There is a need for high throughput molecular sieve compositions made bycrystallization of pre-formed extrudates in a liquid medium comprisingwater under liquid phase crystallization conditions, said molecularsieve compositions having at least one crystalline molecular sieve andoptionally a non-molecular sieve portion. Methods are needed to enablelarge quantities of molecular sieve compositions to be produced withhigher utilization of organic template and silica, while advantageouslygenerating less wastewater as compared to known vapor phase methods.Also, improved methods are needed which minimize post-synthesispurification steps and simplify reactor design. This disclosure meetsthese and other needs.

SUMMARY OF THE INVENTION

This disclosure relates to methods of preparing molecular sievecomposition having at least one crystalline molecular sieve comprisingthe steps of:

-   (a) providing a reaction mixture comprising at least one source of    ions of tetravalent element Y, at least one source of alkali metal    hydroxide, water, optionally at least one seed crystal and/or at    least one source of ions of trivalent element X, the reaction    mixture having the following molar composition:    -   Y:X₂=2 to infinity, preferably from about 2 to about 1000 or 10        to about 1000, more preferably from about 10 to 500 or 15 to        500;    -   OH⁻:Y=0.1 to 1 or 0.001 to 2, preferably from 0.5 to 1;    -   M⁺:Y=0.001 to 2, preferably from 0.5 to 1,    -   wherein M is an alkali metal and the amount of water is at least        sufficient to permit extrusion of the reaction mixture, wherein        one or more embodiments of the reaction mixture is substantially        free of a crystalline molecular sieve;-   (b) extruding the reaction mixture to form a pre-formed extrudate;    and-   (c) crystallizing the pre-formed extrudate in a liquid medium    comprising water under liquid phase crystallization conditions to    form said molecular sieve composition having said crystalline    molecular sieve.

In one or more embodiments of the methods of this disclosure, saidreaction mixture of extruding step (b) further comprises a firstcrystalline molecular sieve, and said crystallizing step (c) furthercomprises a second crystalline molecular sieve in addition to saidmolecular sieve composition having said first crystalline molecularsieve, wherein said second crystalline molecular sieve is different fromsaid first crystalline molecular sieve.

In one or more embodiments, the methods of this disclosure arecharacterized by the first crystalline molecular sieve comprising atleast one of zeolite beta, zeolite Y, mordenite, ZSM-5, ZSM-23, ZSM-11,ZSM-22, ZSM-35 and ZSM-12.

In one or more embodiments, the liquid phase crystallization conditionsare sufficient to substantially convert the pre-formed extrudate tocrystalline molecular sieve. In some embodiments, these methods arecharacterized by the molecular sieve composition which comprises lessabout 20 wt. %, preferably less than 10 wt. %, more preferably less than5 wt. %, of non-crystalline material.

In other embodiments, the molecular sieve composition products of themethods of this disclosure have crush strength measured by theabove-described Mobil Test of less than 9.8 kg/cm, more preferably lessthan 7.2 kg/cm and most preferably less than 5.4 kg/cm.

In preferred embodiments, the reaction mixture has a H₂O:Y ratio in therange of 0.1 to 30 or 0.1 to 10 and preferably 2 to 10.

In some embodiments, the pre-formed extrudate comprises at least onestructure directing agent R. In other embodiments, the liquid mediumcomprises at least one structure directing agent R.

In one aspect, the pre-formed extrudate is submerged in the liquidmedium. In another aspect, the liquid medium is agitated.

In some embodiments, the mixture and/or pre-formed extrudate are exposedto an autogenous pressure in the range of 345 kPa-a to 3450 kPa-a and atemperature of 50° C. to 250° C. during crystallizing step.

In one or more embodiments, the method comprises the additional steps ofwashing and drying the crystalline molecular sieve product. In anotherembodiment, the mixture is dried prior to step (c).

In preferred embodiments, the mixture and/or pre-formed extrudate aresuited to form crystals of molecular sieves of the MCM-22 family,preferably the MCM-22 family molecular sieves comprising at least one ofMCM-22, MCM-49, and MCM-56, under the liquid phase crystallizationconditions.

This disclosure also relates to molecular sieve compositions having atleast one crystalline molecular sieve prepared by any method of thisdisclosure.

This disclosure also relates to a catalyst composition prepared by:

-   (a) providing an extrusion mixture which comprises a molecular sieve    composition having at least one crystalline molecular sieve prepared    by any method of this disclosure, optionally one or more binders,    and optionally one or more extrusion aids; and-   (b) extruding the extrusion mixture to form the catalyst    composition.

This disclosure also relates to a process for converting hydrocarbonscomprising the step of contacting a hydrocarbon feedstock underconversion conditions with a catalyst comprising the molecular sievecomposition having at least one crystalline molecular sieve prepared byany method of this disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A, 1B, 1C, and 1D show XRD patterns of samples made in Examples 1and 2.

FIGS. 2A, 2B, 2C, and 2D show XRD patterns of samples made in Examples 3and 4.

FIGS. 3A and 3B show XRD patterns of samples made in Example 5.

DETAILED DESCRIPTION OF THE INVENTION

The present disclosure relates to methods of preparing molecular sievecompositions, particularly, but not exclusively, to methods forcrystallizing pre-formed extrudates in a liquid medium comprising waterunder liquid phase crystallization conditions, in which the pre-formedextrudates may include a first molecular sieve portion and optionally anon-molecular sieve portion. This method provides a more efficient andsimpler liquid phase crystallization process which produces a largequantity of crystalline such molecular sieve compositions with highutilization of organic template and silica, advantageously generate lesswastewater (e.g., mother liquor) as compared to prior art processes,thereby minimizing effort in purification steps, simplifying reactordesign, and affording the high production throughput. The pre-formedextrudate (including the non-molecular sieve portion when present) issubstantially converted to crystalline molecular sieve.

According to embodiments of this disclosure, there is provided methodsof preparing molecular sieve compositions having at least onecrystalline molecular sieve and methods for preparing the same asdefined by the accompanying claims.

As used in this specification, the term “framework type” is used in thesense described in the “Atlas of Zeolite Framework Types,” 2001.

As used herein, the numbering scheme for the Periodic Table Groups isused as in Chemical and Engineering News, 63(5), 27 (1985).

The term “wppm” as used herein is defined as parts per million byweight.

The term “substantially free” as used herein means less than 5 wt. % andpreferably less than 1 wt. %. For example, the reaction mixture issubstantially free of crystalline molecular sieve means the reactionmixture has less than 5 wt. % and preferably less than 1 wt. %crystalline molecular sieve (not including seed crystals).

The term “substantially converted” as used herein means at least 80 wt.%, preferably at least 85 wt. %, and more preferably at least 90 wt. %converted. For example, the pre-formed extrudate is substantiallyconverted to crystalline molecular sieve means that at least 80 wt. %,preferably at least 85 wt. %, and more preferably at least 90 wt. % ofthe non-crystalline material in the pre-formed extrudate issubstantially converted to crystalline molecular sieve. The crystallizedextrudate normally comprises less about 20 wt. %, preferably less than10 wt. %, and more preferably less than 5 wt. %, of non-crystallinematerial based on the total weight of the pre-formed extrudate.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.

Disclosed are methods of preparing molecular sieve composition having atleast one crystalline molecular sieve comprising the steps of:

-   (a) providing a reaction mixture comprising at least one source of    ions of tetravalent element Y, at least one source of alkali metal    hydroxide, water, optionally at least one seed crystal and/or at    least one source of ions of trivalent element X, the reaction    mixture having the following molar composition:    -   Y:X₂=2 to infinity, preferably from about 2 to about 1000 or 10        to about 1000, more preferably from about 10 to 500 or 15 to        500;    -   OH⁻:Y=0.1 to 1 or 0.001 to 2, preferably from 0.5 to 1;    -   M⁺:Y=0.001 to 2, preferably from 0.5 to 1,    -   wherein M is an alkali metal and the amount of water is at least        sufficient to permit extrusion of the reaction mixture, wherein        in one or more embodiments said reaction mixture is        substantially free of crystalline molecular sieve;-   (b) extruding the reaction mixture to form a pre-formed extrudate;    and-   (c) crystallizing the pre-formed extrudate in a liquid medium    comprising water under liquid phase crystallization conditions to    form said molecular sieve composition having said crystalline    molecular sieve.

The sources of the various elements required in the final product may beany of those in commercial use or described in the literature, as maythe method of preparation of the synthesis mixture.

Y is a tetravalent element selected from Groups 4-14 of the PeriodicTable of the Elements, such as silicon and/or germanium, preferablysilicon. In some embodiments of this disclosure, the source of YO₂comprises solid YO₂, preferably about 30 wt. % solid YO₂ in order toobtain the crystal product of this disclosure. When YO₂ is silica, theuse of a silica source containing preferably about 30 wt. % solidsilica, e.g., silica sold by Degussa under the trade names Aerosil orUltrasil (a precipitated, spray dried silica containing about 90 wt. %silica), an aqueous colloidal suspension of silica, for example one soldby Grace Davison under the trade name Ludox, or HiSil (a precipitatedhydrated SiO₂ containing about 87 wt. % silica, about 6 wt. % free H₂Oand about 4.5 wt. % bound H₂O of hydration and having a particle size ofabout 0.02 micron) favors crystal formation from the above mixture.Preferably, therefore, the YO₂, e.g., silica, source contains about 30wt. % solid YO₂, e.g., silica, and more preferably about 40 wt. % solidYO₂, e.g., silica. The source of silicon may also be a silicate, e.g.,an alkali metal silicate, or a tetraalkyl orthosilicate.

In additional embodiments of this disclosure, the source of YO₂comprises acid of the tetravalent element (Y). When YO₂ is silica, thesilica source may be silicic acid.

X is a trivalent element selected from Groups 3-13 of the Periodic Tableof the Elements, such as aluminum, and/or boron, and/or iron and/orgallium, preferably aluminum. The source of X₂O₃, e.g., aluminum, ispreferably aluminum sulphate, aluminum nitrate or hydrated alumina.Other aluminum sources include, for example, other water-solublealuminum salts, sodium aluminate, or an alkoxide, e.g., aluminumisopropoxide, or aluminum metal, e.g., in the form of chips.

The alkali or alkali earth metal element is advantageously lithium,sodium, potassium, calcium, or magnesium. The source of alkali or alkaliearth metal element is advantageously being metal oxide, metal chloride,metal fluoride, metal sulfate, metal nitrate, or metal aluminate. Thesodium source advantageously is sodium hydroxide or sodium aluminate.The alkali metal may also be replaced by ammonium (NH₄ ⁺) or itsequivalents, e.g., alkyl-ammonium ion.

In a preferred embodiment of the method of this disclosure, thecrystallization is carried out in the presence of a structure directingagent R. Thus in one embodiment, the reaction mixture additionallycomprises R, such that the pre-formed extrudate comprises a structuredirecting agent R. In another embodiment, the structure directing agentR is made available to the crystallization reaction by being containedin the liquid medium but not in the pre-formed extrudate. In yet anotherembodiment the structure directing agent may form part of the reactionmixture used to form the pre-formed extrudate, and a further amount ofstructure directing agent R, may be provided in the liquid mediumseparate from the pre-formed extrudate.

In a preferred embodiment, directing agent R preferably comprises atleast one of cycloalkylamine, azacycloalkane, diazacycloalkane,N,N,N,N′N′N′-hexamethyl-1,5-hexanediaminium (Me₆-diquat-6) salt orN,N,N,N′N′N′-hexamethyl-1,5-pentanediaminium (Me₆-diquat-5) salt, andmixtures thereof, with alkyl preferably comprising from 5 to 8 carbonatoms. Non-limiting examples of R include cyclopentylamine,cyclohexylamine, cycloheptylamine, hexamethyleneimine (HMI),heptamethyleneimine, homopiperazine, and combinations thereof. Examplesof Me₆-diquat-5 salt are hydroxide, chloride, bromide, fluoride,nitrate, sulfate, phosphate, or any mixture thereof. Examples ofMe₆-diquat-6 salt are hydroxide, chloride, bromide, fluoride, nitrate,sulfate, phosphate, or any mixture thereof.

In some embodiments, the directing agent R comprises at least one ofHMI, Me₆-diquat-5 dibromide, Me₆-diquat-5 dichloride, Me₆-diquat-5difluoride, Me₆-diquat-5 diiodide, Me₆-diquat-5 dihydroxide,Me₆-diquat-5 sulfate, Me₆-diquat-5 dinitrate, Me₆-diquat-5 hydroxidebromide, Me₆-diquat-5 hydroxide chloride, Me₆-diquat-5 hydroxidefluoride, Me₆-diquat-5 hydroxide iodide, Me₆-diquat-5 hydroxide nitrate,Me₆-diquat-5 fluoride bromide, Me₆-diquat-5 fluoride chloride,Me₆-diquat-5 fluoride iodide, Me₆-diquat-5 fluoride nitrate,Me₆-diquat-5 chloride bromide, Me₆-diquat-5 chloride iodide,Me₆-diquat-5 chloride nitrate, Me₆-diquat-5 iodide bromide, Me₆-diquat-5bromide nitrate, Me₆-diquat-6 dibromide, Me₆-diquat-6 dichloride,Me₆-diquat-6 difluoride, Me₆-diquat-6 diiodide, Me₆-diquat-6dihydroxide, Me₆-diquat-6 sulfate, Me₆-diquat-6 dinitrate, Me₆-diquat-6hydroxide bromide, Me₆-diquat-6 hydroxide chloride, Me₆-diquat-6hydroxide fluoride, Me₆-diquat-6 hydroxide iodide, Me₆-diquat-6hydroxide nitrate, Me₆-diquat-6 fluoride bromide, Me₆-diquat-6 fluoridechloride, Me₆-diquat-6 fluoride iodide, Me₆-diquat-6 fluoride nitrate,Me₆-diquat-6 chloride bromide, Me₆-diquat-6 chloride iodide,Me₆-diquat-6 chloride nitrate, Me₆-diquat-6 iodide bromide, Me₆-diquat-6bromide nitrate, and any mixtures thereof.

The amount of the directing agent affects the cost and the productquality of the synthesis of a crystalline molecular sieve. The directingagent is generally the most expensive reactant(s) in the hydrothermalreaction mixture of many crystalline molecular sieves. The lower theamount of the directing agent in the hydrothermal reaction mixture, thecheaper the final molecular sieve produced. In one embodiment of thisdisclosure R:YO₂ molar ratio ranges from 0 to 2, preferably from 0.001to 1, more preferably from 0.001 to 0.5, even more preferably from 0.001to 0.3, and most preferably from 0.1 to 0.2. The R:YO₂ molar ratio ismeasured using the total R present in the reaction mixture and theliquid medium.

The composition of the reaction mixture and reaction parameters affectsthe quality and homogeneousness of the product. In preferredembodiments, the composition of the reaction mixture comprises Y:X₂ratio in the range of 2 to infinity, preferably 2 to 1000 or 10 to about1000, and more preferably 10 to 500 or 15 to 500, the OH⁻:Y ratio in therange of 0.001 to 2 and preferably 0.1 to 1 or 0.5 to 1, and the M⁺:Yratio in the range of 0.001 to 2 and preferably 0.1 to 1 or 0.5 to 1.

The amount of water is at least sufficient to permit extrusion to formthe pre-formed extrudates. In some embodiments, the H₂O:Y ratio is inthe range of 0.1 to 50, preferably 0.1 to 30, 1 to 30, more preferablein the range of 2 to 10, alternatively in the range of 4 to 8.

Preferably the reaction mixture includes 0 to about 25 wt. % based ontotal weight of tetrahedral element oxide (e.g., silica) of the reactionmixture, preferably about 1 to about 5 wt. %, seed crystals of themolecular sieve, to facilitate the crystallization reaction. Thefollowing seed crystals, in wt. % based on total weight of tetrahedralelement oxide of the reaction mixture, are useful lower seed crystalswt. % limits for all disclosure processes: 0.001, 0.002, 0.005, 0.01,0.02, 0.05, 0.1, 0.2, 0.5, 1, 2, 5, 10 and 15. The following seedcrystals, in wt. % based on total weight of tetrahedral element oxide ofthe reaction mixture, are useful upper seed crystals wt. % limits forall disclosure processes: 1, 2, 5, 10, 15, 20 and 25. The seed crystalswt. % ideally falls in a range between any one of the above-mentionedlower limits and any one of the above-mentioned upper limits, so long asthe lower limit is less than or equal to the upper limit. The seedcrystals, in wt. % based on total weight of tetrahedral element oxide ofthe reaction mixture, may be present in an amount ranging from 0.001 to25 in one embodiment, alternatively 0.01 to 20, alternatively from 0.1to 10, alternatively 0.5 to 10, alternatively 0.5 to 5, alternativelyand from 0.1 to 5 in another embodiment.

The pre-formed extrudate may also comprise a first molecular sieve. Theamount of the first molecular sieve in the pre-formed extrudate is inthe range of 1 to 99 wt. %, preferably 10 to 50 wt. %, more preferablyin the range of 20 to 50 wt. %.

In one embodiment of this disclosure, the pre-formed extrudate mixturemay be exposed to an autogenous pressure and temperature which allowcrystallization of the mixture under vapor phase conditions. Suitablepressures may be in the range, for example, of from 448 kPa-a to 7.0MPa-a, preferably from 656 kPa-a to 3.6 MPa-a, and more preferably 790kPa-a to 2.17 MPa-a. Suitable temperatures may vary from 50° C. to 500°C., preferably from 80° C. to 250° C., more preferably from 100° C. to250° C. The reactor may comprise an autoclave or any other suitablechamber in which controlled pressure and elevated temperature conditionsfor promoting crystallization can be provided.

Preferably, the crystallization process is carried out with any type ofagitation, e.g., stirring the liquid medium, rotating the pre-formedextrudates, or rotating the vessel about a horizontal axis (tumbling).In some embodiments, the crystallization conditions have the followingagitation rates that are useful agitation rate limits for all disclosureprocesses: 1, 10, 20, 50, 100, 200 and 500 and the following agitationrates that are useful upper agitation rate limits for all disclosureprocesses: 100, 200, 500 and 1000. The agitation rate of thecrystallization conditions ideally falls in a range between any one ofthe above-mentioned lower limits and any one of the above-mentionedupper limits, so long as the lower limit is less than or equal to theupper limit. The agitation rate of the crystallization conditions may bepresent in an amount ranging from 1 to 500 in one embodiment,alternatively 10 to 200, alternatively from 50 to 500, alternatively 20to 500, alternatively 50 to 1000, alternatively and from 10 to 500 inanother embodiment.

Not wishing to be bounded by any theory, we believe that the stirring orcirculation of the liquid medium promote the uniform distribution oforganic template in the liquid medium which results in a more uniformfinal product and less impurities.

In another preferred embodiments of this disclosure, the pre-extrudedmixture is provided within the reactor on a support, the support beingadapted to allow to flowing of liquid medium during crystallization. Thesupport spaces the extrudate from the reactor wall. The support may alsopromote heat circulation during crystallization of the synthesizedmixture.

In preferred embodiments, the pre-extruded synthesis mixture is spacedfrom at least one inner perimeter of the reactor by any suitable meanssuch as the support. The mixture may be spaced from one or more walls.The mixture may also be spaced from a floor of the reactor. Separationof the mixture from the reactor walls promotes removal of the causticagent and enhances heat circulation and promotes exposure of the mixtureto the liquid phase.

The support may be formed by a sieve or grid or mesh. In this way thesupport does not affect the heat circulation whilst allowing efficientremoval of the alkali metal hydroxide caustic agent duringcrystallization.

In preferred embodiments, the tetravalent element is silicon and thesource of ions thereof preferably comprises a source of silica. Thetrivalent element is preferably aluminum and the source of ions thereofpreferably comprises a source of alumina.

The first molecular sieve of the reaction mixture comprises at least oneof a MCM-22 family molecular sieve, ETS-10, ETAS-10, ETGS-10, and amolecular sieve having a zeolite framework type comprising at least oneof ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFX,AFY, AHT, ANA, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AWO, AWW,BCT, *BEA, BEC, BIK, BOG, BPH, BRE, CAN, CAS, CDO, CFI, CGF, CGS, CHA,-CHI, -CLO, CON, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EMT, EON,EPI, ERI, ESV, ETR, EUO, EZT, FAR, FAU, FER, FRA, GIS, GIU, GME, GON,GOO, HEU, IFR, IHW, IMF, ISV, ITE, ITH, ITW, IWR, IWV, IWW, JBW, KFI,LAU, LEV, LIO, -LIT, LOS, LOV, LTA, LTL, LTN, MAR, MAZ, MEI, MEL, MEP,MER, MFI, MFS, MON, MOR, MOZ, MSE, MSO, MTF, MTN, MTT, MTW, MWW, NAB,NAT, NES, NON, NPO, NSI, OBW, OFF, OSI, OSO, OWE, -PAR, PAU, PHI, PON,RHO, -RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAO, SAS, SAT, SAV, SBE,SBS, SBT, SFE, SFF, SFG, SFH, SFN, SFO, SGT, SIV, SOD, SOS, SSY, STF,STI, STT, SZR, TER, THO, TOL, TON, TSC, TUN, UEI, UFI, UOZ, USI, UTL,VET, VFI, VNI, VSV, WEI, -WEN, YUG, and ZON.

In preferred embodiments, the compositions of the reaction mixture formaking molecular sieve compositions having at least one of MCM-22,MCM-49, EMM-10, and MCM-56 may comprise (molar ratios):

-   -   SiO₂/Al₂O₃: 10-500;    -   OH⁻/SiO₂: 0.001-0.5;    -   Na/SiO₂: 0.001-0.5;    -   R/SiO₂: 0.05-0.5; and    -   H₂O/SiO₂: 1-20.

In the case where seed crystals are present, the seed concentration ofthe respective MCM-22, MCM-49 or MCM-56 seed crystals is preferably 0.1to 40 wt. % of the extrudate.

In further embodiments, there is provided a method for preparing acatalyst comprising preparing a molecular sieve according to the methodas hereinbefore described and activating the sieve to form the catalyst.The sieve may be activated for example by water post-treatment of thecrystal and/or by surface modification. Suitable surface modificationmay comprise surface treatment to provide a metal oxide on the catalystsurface such as aluminum oxide.

In yet another embodiments, there is provided a catalyst which is formedfrom molecular sieve compositions having at least one crystallinemolecular sieve produced by the process of this disclosure.

By virtue of the manufacturing method as herein described, the molecularsieves produced and the corresponding catalyst may for example comprisea surface area of at least 300 m²/g preferably at least 500 m²/g andmore preferably at least 600 m²/g, as measured by BET surface areaanalysis using a Tristar 3000 instrument available from MicromeriticsCorporation of Norcoss, Georgia, USA.

The crush strength values as reported herein are measured according tothe Mobil Test using an anvil/strike plate instrument by determining theresistance of formed molecular sieve extrudate to compressive force. Themeasurement is performed on cylindrical extrudate having a length todiameter ratio of at least 1:1 and a length greater than 0.32 cm. Thedetermination is performed by placing the extrudate sample between thedriven anvil and the fixed strike plate of an instrument comprising aWillrich Test Stand in combination with an Ametek Electronic ForceGauge. The Test Stand comprises a movement that holds the Force Gauge,and a strike plate. The strike plate is considerably larger than theanvil, and during testing carries the extrudate pellet under test. Theanvil portion of the instrument comprises a rectangular 0.32 cm×1.27 cmanvil surface arranged to apply compressive force to the pellet carriedon the strike plate during the testing procedure. Prior to performingthe test the minimum gap between opposed surfaces of the anvil andstrike plate is about half the diameter of the cylindrical extrudatepellet.

The sample is prepared by placing the extrudate pellet in a crucible anddrying at 121° C. for at least one hour. This step may be eliminated ifthe sample has been previously dried or calcined. Thereafter, thecrucible containing the sample is placed on a crucible tray which istransferred to a muffle furnace at 538° C. for one hour. Dryingtemperature/time may be altered as appropriate for the material underevaluation. However, consistency in treatment and drying between samplesis imperative. All samples being compared for a given project or familyshould be evaluated after pretreatment at the same temperature/time.After such heating the crucible is removed from the furnace and sealedin a desiccator until cool.

For crush strength determination of a particular molecular sieveproduct, a representative sample of typically 25 cylindrical extrudatepellets is tested. Such pellets, once cooled in the desiccator, areplaced in a Buchner funnel under nitrogen flow. For testing a pellet isremoved from the funnel using tweezers and placed on the strike platedirectly under the raised anvil in a configuration such that thelongitudinal axis of the cylindrical pellet is at 90° to thelongitudinal axis of the 0.32 cm×1.27 cm anvil shoe; with the pelletextending entirely across the 0.32 cm width of the anvil shoe. In thisconfiguration, when under test, the anvil subjects a 0.32 cmlongitudinal portion of the cylinder wall to the applied compressionforce. Once the pellet is in the required configuration, the instrumentis activated such that the anvil is lowered in controlled fashion toapply gradually increasing force to a 0.32 cm contact area along the“spine” of the pellet until the pellet is crushed. The force readingdisplayed on the instrument gauge at the point of collapse of the pelletis recorded. This technique is repeated for the 25 pellets of thesample, and the average measured crush strength value for the molecularsieve over the 25 readings is calculated. This crush strength isreported in normalized fashion as the average applied force per unitlength along the spine of the extrudate to which the anvil sole isapplied. Since the anvil dimension is 0.32 cm the crush strength isreported as force unit (kg) per length unit (cm). Thus, if the measuredforce is, say, 0.91 kg over the 0.32 cm width of the anvil, the crushstrength would be reported as 2.84 kg/cm. As mentioned, the importantfeature of this test method is the comparative crush strength valuesobtained for different molecular sieves.

Preferably the molecular sieve compositions and crystallized extrudateshave crush strength measured by the above-described Mobil Test of lessthan 9.8 kg/cm, more preferably less than 7.2 kg/cm and most preferablyless than 5.4 kg/cm.

The alpha value test is a measure of the cracking activity of a catalystand is described in U.S. Pat. No. 3,354,078 and in the Journal ofCatalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and Vol. 61, p.395 (1980), each incorporated herein by reference as to thatdescription. The experimental conditions of the test used herein includea constant temperature of 538° C. and a variable flow rate as describedin detail in the Journal of Catalysis, Vol. 61, p. 395.

According to other embodiments of this disclosure, there is provided anorganic compound e.g., (hydrocarbon) conversion process comprisingcontacting an organic e.g., hydrocarbon feedstock with a catalyst whichcomprises the molecular sieve compositions described herein underconversion conditions to convert at least a portion of the feedstock toa converted product.

The molecular sieve compositions having at least one crystallinemolecular sieve of this disclosure are useful as catalyst in a widerange of processes, including separation processes and hydrocarbonconversion processes. Specific examples of hydrocarbon conversionprocesses which are effectively catalyzed by these molecular sievecompositions by itself, or in combination with one or more othercatalytically active substances, including for example, othercrystalline molecular sieves, comprise the following:

-   (i) alkylation of aromatic hydrocarbons, e.g., benzene, with long    chain olefins, e.g., C₁₄ olefin, with reaction conditions including,    individually or in any combination, a temperature of from about    340° C. to about 500° C., a pressure of from about 101 to about    20200 kPa-a (absolute), a weight hourly space velocity of from about    2 hr⁻¹ to about 2000 hr⁻¹ and an aromatic hydrocarbon/olefin mole    ratio of from about 1/1 to about 20/1, to provide long chain alkyl    aromatics which can be subsequently sulfonated to provide synthetic    detergents;-   (ii) alkylation of aromatic hydrocarbons with gaseous olefins to    provide short chain alkyl aromatic compounds, e.g., the alkylation    of benzene with propylene to provide cumene, with reaction    conditions including, individually or in any combination, a    temperature of from about 10° C. to about 125° C., a pressure of    from about 101 to about 3030 kPa-a, and an aromatic hydrocarbon    weight hourly space velocity (WHSV) of from 5 hr⁻¹ to about 50 hr⁻¹;-   (iii) alkylation of reformate containing substantial quantities of    benzene and toluene with fuel gas containing C₅ olefins to provide,    inter alia, mono- and di-alkylates with reaction conditions    including, individually or in any combination, a temperature of from    about 315° C. to about 455° C., a pressure of from about 3000 to    about 6000 kPa-a, a WHSV-olefin of from about 0.4 hr⁻¹ to about 0.8    hr⁻¹, a WHSV-reformate of from about 1 hr⁻¹ to about 2 hr⁻¹ and a    gas recycle of from about 1.5 to 2.5 vol/vol fuel gas feed;-   (iv) alkylation of aromatic hydrocarbons, e.g., benzene, toluene,    xylene and naphthalene, with long chain olefins, e.g., C₁₄ olefin,    to provide alkylated aromatic lube base stocks with reaction    conditions including, individually or in any combination, a    temperature of from about 160° C. to about 260° C. and a pressure of    from about 2600 to 3500 kPa-a;-   (v) alkylation of phenols with olefins or equivalent alcohols to    provide long chain alkyl phenols with reaction conditions including,    individually or in any combination, a temperature of from about    200° C. to about 250° C., a pressure of from about 1500 to 2300    kPa-a and a total WHSV of from about 2 hr⁻¹ to about 10 hr⁻¹;-   (vi) conversion of light paraffins to olefins and aromatics with    reaction conditions including, individually or in any combination, a    temperature of from about 425° C. to about 760° C. and a pressure of    from about 170 to about 15000 kPa-a;-   (vii) conversion of light olefins to gasoline, distillate and lube    range hydrocarbons with reaction conditions including, individually    or in any combination, a temperature of from about 175° C. to about    375° C. and a pressure of from about 800 to about 15000 kPa-a;-   (viii) two-stage hydrocracking for upgrading hydrocarbon streams    having initial boiling points above about 260° C. to premium    distillate and gasoline boiling range products in a first stage    using the MCM-22 family molecular sieve of this disclosure in    combination with a Groups 8-10 metal as catalyst with effluent    therefrom being reaction in a second stage using zeolite beta, also    in combination with a Groups 8-10 metal, as catalyst, the reaction    conditions including, individually or in any combination, a    temperature of from about 340° C. to about 455° C., a pressure of    from about 3000 to about 18000 kPa-a, a hydrogen circulation of from    about 176 to about 1760 liter/liter and a liquid hourly space    velocity (LHSV) of from about 0.1 to 10 h⁻¹;-   (ix) a combination hydrocracking/dewaxing process in the presence of    the MCM-22 family molecular sieve of this disclosure and a    hydrogenation component as catalyst, or a mixture of such catalyst    and zeolite beta, with reaction conditions including, individually    or in any combination, a temperature of from about 350° C. to about    400° C., a pressure of from about 10000 to about 11000 kPa-a, an    LHSV of from about 0.4 to about 0.6 and a hydrogen circulation of    from about 528 to about 880 liter/liter;-   (x) reaction of alcohols with olefins to provide mixed ethers, e.g.,    the reaction of methanol with isobutene and/or isopentene to provide    methyl-t-butyl ether (MTBE) and/or t-amyl methyl ether (TAM) with    conversion conditions including, individually or in any combination,    a temperature of from about 20° C. to about 200° C., a pressure of    from 200 to about 20000 kPa-a, a WHSV (gram-olefin per hour    gram-zeolite) of from about 0.1 hr⁻¹ to about 200 hr⁻¹ and an    alcohol to olefin molar feed ratio of from about 0.1/1 to about 5/1;-   (xi) toluene disproportionation with C₉+ aromatics as co-feed with    reaction conditions including, individually or in any combination, a    temperature of from about 315° C. to about 595° C., a pressure of    from about 101 to about 7200 kPa-a, a hydrogen/hydrocarbon mole    ratio of from about 0 (no added hydrogen) to about 10 and a WHSV of    from about 0.1 hr⁻¹ to about 30 hr⁻¹;-   (xii) preparation of the pharmaceutically-active compound    2-(4-isobutylphenyl) propionic acid, i.e. ibuprofen, by reacting    isobutyl benzene with propylene oxide to provide the intermediate    2-(4-isobutylphenyl) propanol followed by oxidation of the alcohol    to the corresponding carboxylic acid;-   (xiii) use as an acid-binding agent in the reaction of amines with    heterocyclic fiber-reactive components in preparation of dyes to    prepare practically salt-free reactive dye-containing solution, as    in German Patent No. DE 3,625,693, incorporated entirely herein by    reference;-   (xiv) as the absorbent for separating 2,6-toluene diisocyanate    (2,6-TDI) from isomers if TDI as in U.S. Pat. No. 4,721,807,    incorporated entirely herein by reference, whereby a feed mixture    comprising 2,6-TDI and 2,4-TDI is contacted with the present MCM-22    family molecular sieve which has been cation-exchanged with K ions    to absorb the 2,6-TDI, followed by recovering the 2,6-TDI by    desorption with desorbent material comprising toluene;-   (xv) as the absorbent for separating 2,4-TDI from its isomers as in    U.S. Pat. No. 4,721,806, incorporated entirely herein by reference,    whereby a feed mixture comprising 2,4-TDI and 2,6-TDI is contact    with the present MCM-22 family molecular sieve which has been    cation-exchanged with Na, Ca Li and/or Mg ions to absorb the    2,4-TDI, followed by recovering the 2,4-TDI by desorption with    desorbent material comprising toluene;-   (xvi) in a process for decreasing the durene content of a 90-200°    C.+ bottoms fraction obtained from the catalytic conversion of    methanol to gasoline which comprises contacting the    durene-containing bottoms fraction with hydrogen over a catalyst of    the present MCM-22 family molecular sieve with a hydrogenation    metal, at conditions including, individually or in any combination,    a temperature of from about 230° C. to about 425° C. and a pressure    of from about 457 to about 22000 kPa-a;-   (xvii) in a processes for co-producing phenol and ketones that    proceed through benzene alkylation, followed by formation of the    alkylbenzene hydroperoxide and cleavage of the alkylbenzene    hydroperoxide into phenol and ketone, e.g., benzene and propylene to    phenol and acetone, benzene and C₄ olefins to phenol and methyl    ethyl ketone, such as those described for example in international    application PCT/EP2005/008557, which can be followed by conversion    of phenol and acetone to bis-phenol-A as described in international    application PCT/EP2005/008554, benzene to phenol and cyclohexanone,    or benzene and ethylene to phenol and methyl ethyl ketone, as    described for example in PCT/EP2005/008551;-   (xviii) in a process of benzene alkylation reactions where    selectivity to the monoalkylbenzene is required, e.g., selectively    sec-butylbenzene from benzene and C₄ olefin feeds that are rich in    linear butenes, as described in international application    PCT/EP2005/008557, preferably, this conversion is carried out by    co-feeding benzene and the C₄ olefin feed with the catalyst of the    present invention, at a temperature of about 60° C. to about 260°    C., for example of about 100° C. to 200° C., a pressure of 7000    kPa-a or less, and a feed weight hourly space velocity (WHSV) based    on C₄ alkylating agent of from about 0.1 to 50 h⁻¹ and a molar ratio    of benzene to C₄ alkylating agent from about 1 to about 50; and-   (xix) in a process for transalkylations, such as, for example,    polyalkylbenzene transalkylations.

In the case of many catalysts, it is desirable to incorporate themolecular sieve compositions having at least one crystalline molecularsieve with another material resistant to the temperatures and otherconditions employed in organic conversion processes. Such materialsinclude active and inactive materials and synthetic or naturallyoccurring zeolites as well as inorganic materials such as clays, silicaand/or metal oxides such as alumina. The latter may be either naturallyoccurring or in the form of gelatinous precipitates or gels includingmixtures of silica and metal oxides. Use of a material in conjunctionwith the molecular sieve compositions of this disclosure, i.e. combinedtherewith or present during synthesis of the molecular sievecompositions, which are active, tends to change the conversion and/orselectivity of the catalyst in certain organic conversion processes.Inactive materials suitably serve as diluents to control the amount ofconversion in a given process so that products can be obtainedeconomically and orderly without employing other means for controllingthe rate of reaction. These materials may be incorporated into naturallyoccurring clays, e.g., bentonite and kaolin, to improve the crushstrength of the catalyst under commercial operating conditions. Thematerials, i.e. clays, oxides, etc., function as binders for thecatalyst. It is desirable to provide a catalyst having good crushstrength because in commercial use it is desirable to prevent thecatalyst from breaking down into powder-like materials. These claybinders have been employed normally only for the purpose of improvingthe crush strength of the catalyst.

Naturally occurring clays which can be composited with the molecularsieve compositions include the montmorillonite and kaolin family, whichfamilies include the subbentonites, and the kaolins commonly known asDixie, McNamee, Georgia and Florida clays or others in which the mainmineral constituent is halloysite, kaolinite, dictite, narcite, oranauxite. Such clays can be used in the raw state as originally mined orinitially subjected to calcination, acid treatment or chemicalmodification. Binders useful for compositing with the present dualmolecular sieve composition also include inorganic oxides, notablyalumina.

In addition to the foregoing materials, the molecular sieve compositioncan be composited with a porous matrix material such as silica-alumina,silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia,silica-titania as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesiaand silica-magnesia-zirconia.

The relative proportions of molecular sieve compositions and inorganicoxide matrix vary widely, with the content of the molecular sievecompositions ranging from about 1 to about 99 percent by weight and moreusually, particularly when the composite is prepared in the form ofbeads, in the range of about 20 to about 80 wt. % of the composite.

In one or more numbered embodiments, this disclosure relates to:

-   1. A method of preparing a molecular sieve composition having at    least one crystalline molecular sieve comprising the steps of:-   a. providing a reaction mixture comprising at least one source of    ions of tetravalent element Y, at least one source of alkali metal    hydroxide, water, optionally at least one seed crystal, and    optionally at least one source of ions of trivalent element X, said    reaction mixture having the following molar composition:    -   Y:X₂=2 to infinity    -   OH⁻:Y=0.001 to 2    -   M⁺:Y=0.001 to 2        wherein M is an alkali metal and the amount of water is at least        sufficient to permit extrusion of said reaction mixture, wherein        in one or more embodiments said reaction mixture is        substantially free of crystalline molecular sieve (not including        the optional seed crystals);-   b. extruding said reaction mixture to form a pre-formed extrudate;    and-   c. crystallizing said pre-formed extrudate in a liquid medium    comprising water under liquid phase crystallization conditions to    form said molecular sieve composition having said crystalline    molecular sieve.-   2. The method according to embodiment 1, characterized by said    pre-formed extrudate comprising a structure directing agent R.-   3. The method according to any preceding embodiment, characterized    by said liquid medium comprising structure directing agent R.-   4. The method according to any preceding embodiment, characterized    by said pre-formed extrudate being submerged in said liquid medium.-   5. The method according to any preceding embodiment, characterized    by said liquid medium being agitated.-   6. The method according to any preceding embodiment, characterized    by said crystallized extrudate comprises less than 20 wt. % of    non-crystalline materials.-   7. The method according to any preceding embodiment, characterized    by said crystallized extrudates having a crush strength less than    9.8 kg/cm.-   8. The method according to any preceding embodiment, characterized    by the method comprising the additional steps of washing and drying    the crystalline molecular sieve product.-   9. The method according to any preceding embodiment, characterized    by the mixture being dried prior to performing step (c).-   10. The method according to any preceding embodiment, characterized    by the mixture being exposed to an autogenous pressure in the range    of 345 kPa-a to 3450 kPa-a and a temperature of 50° C. to 250° C.    during crystallizing step.-   11. The method according to any preceding embodiment, characterized    by the Y:X₂ ratio being from 2 to 1000.-   12. The method according to any preceding embodiment, characterized    by the H₂O:Y ratio being from 0.1 to 300.-   13. The method according to any preceding embodiment, the OH⁻:Y    ratio being from 0.1 to 1.-   14. The method according to any preceding embodiment, characterized    by the M⁺:Y ratio being from 0.01 to 2.-   15. The method according to any preceding embodiment, characterized    by the mixture being suited to form crystals of molecular sieves of    the MCM-22 family under said liquid phase crystallization    conditions.-   16. The method according to embodiment 15, characterized by the    MCM-22 family molecular sieves comprising at least one of MCM-22,    MCM-49, and MCM-56.-   17. The method according to any preceding embodiment, characterized    by the tetravalent element comprising silicon.-   18. The method according to any preceding embodiment, characterized    by the trivalent element comprising aluminum.-   19. The method of any preceding embodiment, wherein said reaction    mixture of extruding step (b) further comprises a first crystalline    molecular sieve, said molecular sieve composition of crystallizing    step (c) further comprises a second crystalline molecular sieve, and    said second crystalline molecular sieve is different from said first    crystalline molecular sieve.-   20. The method of any preceding embodiment, characterized by the    first crystalline molecular sieve comprising at least one of zeolite    beta, zeolite Y, mordenite, ZSM-5, ZSM-23, ZSM-11, ZSM-22, ZSM-35    and ZSM-12.-   21. A crystalline molecular sieve prepared by any preceding    embodiment.-   22. A process for converting hydrocarbons comprising the step of    contacting a hydrocarbon feedstock under conversion conditions with    a crystalline molecular sieve of embodiment 21.

Embodiments of this disclosure will now be described in the followingExamples to further illustrate this disclosure.

EXPERIMENTAL Preparation of HMI-Free Aluminosilicate Pre-FormedExtrudate

Aluminosilicate pre-formed extrudates were prepared from a mixture of908 grams of Ultrasil silica, 180 grams of sodium aluminate solution (45wt. %), and 104 grams of 50 wt. % sodium hydroxide solution, 1080 gramsof DI water, and 40 grams of MCM-22 seed crystals. The mixture had thefollowing molar composition:

SiO₂/Al₂O₃=29.4

H₂O/SiO₂=4.54

OH⁻/SiO₂=0.17

Na⁺/SiO₂=0.17

The mixture was mulled and formed into 1.59 mm cylinder extrudates. Thewet extrudates were then stored in a sealed container before use. Driedextrudates were prepared separately by drying the wet extrudates in anoven at 120° C. for 2 hrs.

Example 1

Five hundred grams of dried extrudates were placed in an autoclave withwire mesh support. A mixture of 300 grams of DI water and 1235 grams ofHMI was added to cover the extrudates.

The extrudates were crystallized at 171° C. for 24 hrs. After thereaction, the product was discharged, washed with water, and dried at121° C. XRD patterns of the top and bottom samples collected from theextrudate bed showed the typical pure phase of MCM-22 topology at topand low crystallinity with trace of impurities at bottom, see FIGS. 1A &B. The uneven distribution of HMI was believed to be the reason for thisresult. The resulting extrudates showed a relatively low crush strength.

Example 2

One thousand and sixty grams of wet extrudates were placed in anautoclave with wire mesh support. A mixture of 657 grams of DI water and200 grams of HMI was added to cover the extrudates.

The extrudates were crystallized at 171° C. for 24 hrs. After thereaction, the product was discharged, washed with water, and dried at121° C. XRD patterns of the top and bottom samples, collected from thecharged extrudate bed, showed the typical pure phase of MCM-22 topologyat top and low crystallinity with trace of impurities at bottom, seeFIGS. 1C & D. The uneven distribution of HMI was believed to be thereason for this result. The resulting extrudates showed a relatively lowcrush strength.

Example 3

One hundred fifteen grams of pre-formed dried extrudates were placed ina 600 ml autoclave with wire mesh support. The distance between thebottom of the autoclave and wire mesh support is greater than 12.7 mm. Amechanical stir was installed to stir the liquid medium. A mixture of330 grams of DI water and 50 grams of HMI was added to cover the chargedextrudates.

The extrudates were crystallized at 171° C. for 24 hrs at 150 rpm. Afterthe reaction, the product was discharged, washed with water, and driedat 121° C. The XRD pattern of the as-synthesized materials from top andbottom showed the typical pure phase of MCM-22, see FIGS. 2 A & B. TheSEM of the as-synthesized material showed that the material was composedof agglomerates of MCM-22 platelet crystals. The addition of stirringshowed a significant improvement in product quality due to the bettercirculation of the HMI/water mixture inside the autoclave. Calcinedextrudate had a surface area of 610 m²/g and Si/Al₂ ratio of 24.3. Theresulting extrudates showed a relatively low crush strength.

Example 4

Two hundred grams of pre-formed wet extrudates were placed in a 600 mlautoclave with wire mesh support. The distance between the bottom of theautoclave and wire mesh support is greater than 12.7 mm. A mechanicalstir was installed to stir the liquid medium. A mixture of 265 grams ofDI water and 50 grams of HMI was added to cover the charged extrudates.

The extrudates were crystallized at 171° C. for 24 hrs at 150 rpm. Afterthe reaction, the product was discharged, washed with water, and driedat 121° C. The XRD pattern of the as-synthesized materials from top andbottom showed the typical phase of MCM-22, see FIGS. 2 C & D. The SEM ofthe as-synthesized material showed that the material was composed ofagglomerates of MCM-22 platelet crystals. The addition of stirringshowed a significant improvement in product quality due to the bettercirculation of the HMI/water mixture inside the autoclave. Calcinedextrudate had a surface area of 578 m²/g and Si/Al₂ ratio of 24.5. Theresulting extrudates showed a relatively low crush strength.

Example 5

Six hundred thirty-five (635) grams of wet pre-formed wet extrudateswere placed in an autoclave with wire mesh support. The distance betweenbottom of autoclave and wire mesh support is greater than 12.7 mm. Amixture of 200 grams HMI and 981 grams DI water was added into theautoclave to cover the charged extrudates.

The extrudates were crystallized at 171° C. for 24 hrs at 150 rpm. Afterthe reaction, the product was discharged, washed with water, and driedat 121° C. The XRD pattern of the calcined products, extrudate andpowder, showed the typical phase of MCM-22, see FIGS. 3 A & B, and theresulting powders did show a small trace of impurities. The SEM of theas-synthesized material showed that the material was composed ofagglomerates of MCM-22 platelet crystals. The addition of stirringshowed a significant improvement in product quality due to the bettercirculation of the HMI/water mixture inside the autoclave. Calcinedextrudate had a surface area of 608 m²/g and Si/Al₂ ratio of ˜24.5. Theas-synthesized extrudates were pre-calcined in nitrogen at 482° C. for 3hrs and then were converted into the hydrogen form by threeion-exchanges with ammonium nitrate solution at room temperature,followed by drying at 120° C., and calcination at 540° C. for 6 hours.The resulting exchanged extrudate shows an Alpha value of 800. Theresulting extrudates showed a relatively low crush strength.

Preparation of Beta/MCM-22 Pre-Formed Extrudates Example 6

Pre-formed extrudates containing zeolite beta and MCM-22 were preparedfrom a mixture of 454 grams of Ultrasil silica, 250 grams of zeolitebeta crystal, 165 grams of HMI, 90 grams of sodium aluminate solution(45%), and 52 grams of 50% sodium hydroxide solution, 500 grams of DIwater, and 20 grams of MCM-22 seed crystals. The mixture had thefollowing molar composition:

SiO₂/Al₂O₃=30.1

H₂O/SiO₂=5.7

OH⁻/SiO₂=0.17

Na⁺/SiO₂=0.17

HMI/SiO₂=0.24

The ratio of zeolite beta crystal/Ultrasil silica was approximately35/65 on a weight basis. The mixture was then mulled and formed into1.59 mm cylindrical extrudates using a mini-extruder. The extrudateswere then stored in a sealed container before use.

The pre-formed wet extrudates were placed in a 2-liter autoclave withwire mesh support. Additional HMI and DI water were added into theautoclave to cover the charged extrudates. The distance between bottomof autoclave and wire mesh support is greater than 12.7 mm.

The extrudates were crystallized at 171° C. for 36 hrs at 150 ppm. Afterthe reaction, the product was discharged, washed with water, and driedat 121° C. The XRD pattern of the as-synthesized material showed thetypical mixed phases of MCM-22 and zeolite beta with Ferrieriteimpurity. The SEM of the as-synthesized material showed that thematerial was composed of layers morphology of MCM-22 platelet crystals,sphere-like beta crystals, and rod-like Ferrierite crystals. Surfacearea of calcined product was 502 m²/g.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.

The meanings of terms used herein shall take their ordinary meaning inthe art; reference shall be taken, in particular, to Handbook ofPetroleum Refining Processes, Third Edition, Robert A. Meyers, Editor,McGraw-Hill (2004). In addition, all patents and patent applications,test procedures (such as ASTM methods), and other documents cited hereinare fully incorporated by reference to the extent such disclosure is notinconsistent with this invention and for all jurisdictions in which suchincorporation is permitted. Also, when numerical lower limits andnumerical upper limits are listed herein, ranges from any lower limit toany upper limit are contemplated. Note further that Trade Names usedherein are indicated by a ™ symbol or ® symbol, indicating that thenames may be protected by certain trademark rights, e.g., they may beregistered trademarks in various jurisdictions.

While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of theinvention. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present invention,including all features which would be treated as equivalents thereof bythose skilled in the art to which the invention pertains.

1. A method of preparing a molecular sieve composition having at least one crystalline molecular sieve comprising the steps of: a. providing a reaction mixture comprising at least one source of ions of tetravalent element Y, at least one source of alkali metal hydroxide, water, optionally at least one seed crystal, and optionally at least one source of ions of trivalent element X, said reaction mixture having the following molar composition: Y:X₂=2 to infinity OH⁻:Y=0.001 to 2 M⁺:Y=0.001 to 2  wherein M is an alkali metal and the amount of water is at least sufficient to permit extrusion of said reaction mixture, wherein said reaction mixture is substantially free of a crystalline molecular sieve (not including the optional seed crystals); b. extruding said reaction mixture to form a pre-formed extrudate; and c. crystallizing said pre-formed extrudate in a liquid medium comprising water under liquid phase conditions to form said molecular sieve composition having said crystalline molecular sieve.
 2. The method according to claim 1, characterized by said pre-formed extrudate comprising a structure directing agent R.
 3. The method according to claim 1, characterized by said liquid medium comprising structure directing agent R.
 4. The method according to claim 1, characterized by said pre-formed extrudate being submerged in said liquid medium.
 5. The method according to claim 1, characterized by said liquid medium being agitated.
 6. The method according to claim 1, characterized by said crystallized extrudate comprises less than 20 wt. % of non-crystalline materials.
 7. The method according to claim 1, characterized by said crystallized extrudates having a crush strength less than 9.8 kg/cm.
 8. The method according to claim 1, characterized by the method comprising the additional steps of washing and drying the crystalline molecular sieve product.
 9. The method according to claim 1, characterized by the mixture being dried prior to performing step (c).
 10. The method according to claim 1, characterized by the mixture being exposed to an autogenous pressure in the range of 345 kPa-a to 3450 kPa-a and a temperature of 50° C. to 250° C. during crystallizing step.
 11. The method according to claim 1, characterized by the Y:X₂ ratio being about 2 to about
 1000. 12. The method according to claim 1, characterized by the H₂O:Y ratio being 0.1 to
 30. 13. The method according to claim 1, the OH⁻:Y ratio being 0.1 to
 1. 14. The method according to claim 1, characterized by the mixture being suited to form crystals of molecular sieves of the MCM-22 family under said liquid phase crystallization conditions.
 15. The method according to claim 14, characterized by the MCM-22family molecular sieves comprising at least one of MCM-22, MCM-49, and MCM-56.
 16. The method according to claim 1, characterized by the tetravalent element comprising silicon.
 17. The method according to claim 1, characterized by the trivalent element comprising aluminum.
 18. The method according to claim 1, wherein said reaction mixture of said extruding step (b) further comprises a first crystalline molecular sieve, said molecular sieve composition of crystallizing step (c) further comprises a second crystalline molecular sieve, and said second crystalline molecular sieve is different from said first crystalline molecular sieve.
 19. The method of claim 18, characterized by the first crystalline molecular sieve comprising at least one of zeolite beta, zeolite Y, mordenite, ZSM-5, ZSM-23, ZSM-11, ZSM-22, ZSM-35 and ZSM-12. 